Palladium-Catalyzed α-Arylation of Carboxylic Acids and Secondary Amides via a Traceless Protecting Strategy.

A novel traceless protecting strategy is presented for the long-standing challenge of conducting the palladium-catalyzed α-arylation of carboxylic aids and secondary amides with aryl halides. Both of the presented coupling processes occur with a variety of carboxylic acids and amides and with a variety of aryl bromides containing a broad range of functional groups, including base-sensitive functionality like acyl, alkoxycarbonyl, nitro, cyano, and even hydroxyl groups. Five commercial drugs were prepared through this method in one step in 81-96% yield. Gram-scale synthesis of medication Naproxen and Flurbiprofen with low palladium loading further highlights the practical value of this method

Stereodivergent Construction of Tertiary Fluorides in Vicinal Stereogenic Pairs by Allylic Substitution with Iridium and Copper Catalysts.

Although much effort has been spent on the enantioselective synthesis of tertiary alkyl fluorides, the synthesis of compounds containing such a stereogenic center within an array of stereocenters, particularly two vicinal ones, remains a synthetic challenge, and no method to control the configuration of each stereogenic center independently has been reported. We describe a strategy to achieve such a stereodivergent synthesis of vicinal stereogenic centers, one containing a fluorine atom, by forming the connecting carbon-carbon bond with a catalyst system comprising an iridium complex that controls the configuration at the electrophilic carbon and a copper catalyst that controls the configuration at the nucleophilic fluorine-containing carbon. These reactions occur with alkyl- and aryl-substituted allylic esters and the unstabilized enolates of azaaryl ketones, esters, and amides in high yield, diastereoselectivity, and enantioselectivity (generally >90% yield, >20:1 dr, 97-99% ee). Access to all four stereoisomers of products demonstrates the precise control of the two configurations independently. This methodology extends to the stereodivergent construction of vicinal quaternary and tertiary stereocenters in similarly high yield and selectivity. DFT calculations uncover the origin of stereoselectivity of copper enolate in allylic substitution

Trimethylphosphate as a Methylating Agent for Cross Coupling: A Slow-Release Mechanism for the Methylation of Arylboronic Esters.

A methyl group on an arene, despite its small size, can have a profound influence on biologically active molecules. Typical methods to form a methylarene involve strong nucleophiles or strong and often toxic electrophiles. We report a strategy for a new, highly efficient, copper and iodide co-catalyzed methylation of aryl- and heteroarylboronic esters with the mild, nontoxic reagent trimethylphosphate, which has not been used previously in coupling reactions. We show that it reacts in all cases tested in yields that are higher than those of analogous copper-catalyzed reactions of MeOTs or MeI. The combination of C-H borylation and this methylation with trimethylphosphate provides a new approach to the functionalization of inert C-H bonds and is illustrated by late-stage methylation of four medicinally active compounds. In addition, reaction on a 200 mmol scale demonstrates reliability of this method. Mechanistic studies show that the reaction occurs by a slow release of methyl iodide by reaction of PO(OMe)3 with iodide catalyst, rather than the typical direct oxidative addition to a metal center. The low concentration of the reactive electrophile enables selective reaction with an arylcopper intermediate, rather than nucleophilic groups on the arylboronate, and binding of tert-butoxide to the boronate inhibits reaction of the electrophile with the tert-butoxide activator to form methyl ether

Vanishing Effective Mass of the Neutrinoless Double Beta Decay?

We stress that massive neutrinos may be Majorana particles even if the effective mass of the neutrinoless double beta decay m_ee vanishes. We show that current neutrino oscillation data do allow m_ee = 0 to hold, if the Majorana CP-violating phases lie in two specific regions. Strong constraints on three neutrino masses can then be obtained. We find that the neutrino mass spectrum performs a normal hierarchy: m_1 < m_2 < m_3. A possible texture of the neutrino mass matrix is also illustrated under the m_ee = 0 condition.Comment: RevTex 9 pages (2 PS figures included). More discussions and references added. Results partly changed. To appear in Phys. Rev.

Analysis of the doubly heavy baryons in the nuclear matter with the QCD sum rules

In this article, we study the doubly heavy baryon states $\Xi_{cc}$, $\Omega_{cc}$, $\Xi_{bb}$ and $\Omega_{bb}$ in the nuclear matter using the QCD sum rules, and derive three coupled QCD sum rules for the masses, vector self-energies and pole residues. The predictions for the mass-shifts in the nuclear matter $\Delta M_{\Xi_{cc}}=-1.11\,\rm{GeV}$, $\Delta M_{\Omega_{cc}}=-0.33\,\rm{GeV}$, $\Delta M_{\Xi_{bb}}=-3.37\,\rm{GeV}$ and $\Delta M_{\Omega_{bb}}=-1.05\,\rm{GeV}$ can be confronted with the experimental data in the future.Comment: 10 pages, 4 figure

Arsenic and Fluoride Exposure in Drinking Water: Children’s IQ and Growth in Shanyin County, Shanxi Province, China

BACKGROUND: Recently, in a cross-sectional study of 201 children in Araihazar, Bangladesh, exposure to arsenic (As) in drinking water has been shown to lower the scores on tests that measure children’s intellectual function before and after adjustment for sociodemographic features. OBJECTIVES: We investigated the effects of As and fluoride exposure on children’s intelligence and growth. METHODS: We report the results of a study of 720 children between 8 and 12 years of age in rural villages in Shanyin county, Shanxi province, China. The children were exposed to As at concentrations of 142 ± 106 μg/L (medium-As group) and 190 ± 183 μg/L (high-As group) in drinking water compared with the control group that was exposed to low concentrations of As (2 ± 3 μg/L) and low concentrations of fluoride (0.5 ± 0.2 mg/L). A study group of children exposed to high concentrations of fluoride (8.3 ± 1.9 mg/L) but low concentrations of As (3 ± 3 μg/L) was also included because of the common occurrence of elevated concentrations of fluoride in groundwater in our study area. A standardized IQ (intelligence quotient) test was modified for children in rural China and was based on the classic Raven’s test used to determine the effects of these exposures on children’s intelligence. A standardized measurement procedure for weight, height, chest circumference, and lung capacity was used to determine the effects of these exposures on children’s growth. RESULTS: The mean IQ scores decreased from 105 ± 15 for the control group, to 101 ± 16 for the medium-As group (p < 0.05), and to 95 ± 17 for the high-As group (p < 0.01). The mean IQ score for the high-fluoride group was 101 ± 16 and significantly different from that of the control group (p < 0.05). Children in the control group were taller than those in the high-fluoride group (p < 0.05); weighed more than the those in the high-As group (p < 0.05); and had higher lung capacity than those in the medium-As group (p < 0.05). CONCLUSIONS: Children’s intelligence and growth can be affected by high concentrations of As or fluoride. The IQ scores of the children in the high-As group were the lowest among the four groups we investigated. It is more significant that high concentrations of As affect children’s intelligence. It indicates that arsenic exposure can affect children’s intelligence and growth

Impacts of the Higgs mass on vacuum stability, running fermion masses and two-body Higgs decays

The latest results of the ATLAS and CMS experiments indicate 116 GeV \lesssim M_H \lesssim 131 GeV and 115 GeV \lesssim M_H \lesssim 127 GeV, respectively, for the mass of the Higgs boson in the standard model (SM) at the 95% confidence level. In particular, both experiments point to a preferred narrow mass range M_H \simeq (124 ... 126) GeV. We examine the impact of this preliminary result of M_H on the SM vacuum stability by using the two-loop renormalization-group equations (RGEs), and arrive at the cutoff scale \Lambda_VS \sim 4 \times 10^{12} GeV (for M_H = 125 GeV, M_t = 172.9 GeV and \alpha_s(M_Z) = 0.1184) where the absolute stability of the SM vacuum is lost and some kind of new physics might take effect. We update the values of running lepton and quark masses at some typical energy scales, including the ones characterized by M_H, 1 TeV and \Lambda_VS, with the help of the two-loop RGEs. The branching ratios of some important two-body Higgs decay modes, such as H \to b\bar{b}, H \to \tau^+ \tau^-, H\to \gamma\gamma, H\to W^+ W^- and H \to Z Z, are also recalculated by inputting the values of relevant particle masses at M_H.Comment: RevTex 14 pages, 4 figures; the treatment of vacuum stability improved, references update

Review: optical fiber sensors for civil engineering applications

Optical fiber sensor (OFS) technologies have developed rapidly over the last few decades, and various types of OFS have found practical applications in the field of civil engineering. In this paper, which is resulting from the work of the RILEM technical committee “Optical fiber sensors for civil engineering applications”, different kinds of sensing techniques, including change of light intensity, interferometry, fiber Bragg grating, adsorption measurement and distributed sensing, are briefly reviewed to introduce the basic sensing principles. Then, the applications of OFS in highway structures, building structures, geotechnical structures, pipelines as well as cables monitoring are described, with focus on sensor design, installation technique and sensor performance. It is believed that the State-of-the-Art review is helpful to engineers considering the use of OFS in their projects, and can facilitate the wider application of OFS technologies in construction industry